Refrigerant mixture comprising difluoromethane and 1,1,1-trifluoroethane

ABSTRACT

A refrigerant composition useful as a substitute for chlorodifluoromethane (CHClF 2 , HCFC-22). The refrigerant composition has a first constituent of difluoromethane (CH 2 F 2 , HFC-32); a second constituent of 1,1,1-trifluoroethane (CH 3 CF 3 ; namely, HFC-143a); and a third constituent selected from cyclopropane (C 3 H 6 , RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF 3 CHFCF 3 , HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH 3 CF 2 CF 3 , HFC-245cb), 1,1,1,2,3,3-hexafluoropropane (CHF 2 CHFCF 3 , HFC-236ea), butane (C 4 H 10 , R-600), bis(difluoromethyl)ether (CHF 2 OCHF 2 , HFE-134) and pentafluoroethylmethylether (CF 3 CF 2 OCH 3 , HFE-245).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a refrigerant mixture which is useful as a substitute for chlorodifluoromethane (CHClF₂, HCFC-22). More particularly, the present invention relates to a refrigerant mixture which is useful as a substitute for HCFC-22, which comprises a first constituent of difluoromethane (CH₂F₂, HFC-32); a second constituent of 1,1,1-trifluoroethane (CH₃CF₃, HFC-143a); and a third constituent selected from the group consisting of cyclopropane (C₃H₆, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF₃CHFCF₃, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH₃CF₂CF₃, HFC-245cb), 1,1,1,2,3,3-hexafluoropropane (CHF₂CHFCF₃, HFC-236ea), butane (C₄H₁₀, R-600), bis(difluoromethyl)ether (CHF₂OCHF₂, HFE-134) and pentafluoroethylmethylether (CF₃CF₂OCH₃, HFE-245).

2. Description of the Prior Art

As it is well known, CFC compounds have been restricted in production and use in accordance with the Montreal Protocol because they have been found as a main factor in contributing to the destruction of the ozone layer. In advanced nations, the use of such CFC compounds has already been banned since 1996. It is also known that HCFC-based compounds such as HCFC-22 have considerable effects in causing damage to the ozone layer even though this effect is less severe than those of the CFC compounds. For this reason, a restriction has been made to gradually reduce the use of such HCFC-based compounds. A plan has also been made to ban the use of HCFC-based compounds about the year 2020.

This has resulted in a number of world-wide research efforts to produce substitute materials coping with the restriction in use of HCFC-22 which will be more severe in the future. The representative examples of a substitute refrigerant mixtures are HFC-407C and HFC-410A proposed by the American Society of Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE). HFC-407C is a refrigerant mixture of HFC-32/125/134a in a ratio of 23/25/52 (based on weight percent). Meanwhile, HFC-410A is a refrigerant mixture of HFC-32/125 in a ratio of 50/50 (based on weight percent).

In addition, U.S. Pat. No. 5,080,823 discloses a mixed refrigerant composition of HFC-143a/propane (C₃H₈), U.S. Pat. No. 5,185,094: HFC-32/125/134a, U.S. Pat. No. 5,211,867: HFC-125/143a, U.S. Pat. No. 5,234,613: HFC-32/propane, U.S. Pat. No. 5,236,611: PFC-218/HFC-143a, U.S. Pat. No. 5,290,466: HFC-32/134a/134, U.S. Pat. No. 5,340,490: HFC-23/CO₂ or HFC-23/116/CO₂, U.S. Pat. No. 5,403,504: HFC-125/32, U.S. Pat. No. 5,429,760: HFC-23/134a, U.S. Pat. No. 5,538,660: HFC-32/HFC-134a/FC-14 or HFC-32/HFC-134a/PFC-218, and U.S. Pat. No. 5,643,492: HFC-32/125/134a.

Also, Japanese Patent Laid-open Publication No. 172386/1991 discloses a mixed refrigerant composition of HFC-32/125/152, Japanese Patent Laid-open Publication No. 170594/1991: HFC-23/125/134a, Japanese Patent Laid-open Publication No. 170592/1991: HFC-32/143a/152a, Japanese Patent Laid-open Publication No. 170593/1991: HFC-23/125/32, Japanese Patent Laid-open Publication No. 170591/1991: HFC-23/143a/134a, Japanese Patent Laid-open Publication No. 170590/1991: HFC-125/134a/32, Japanese Patent Laid-open Publication No. 170589/1991: HFC-23/143a/152a, Japanese Patent Laid-open Publication No. 170588/1991: HFC-125/143a/134a, Japanese Patent Laid-open Publication No. 170587/1991: HFC-32/134a/152a, Japanese Patent Laid-open Publication No. 170586/1991: HFC-32/143a/134a, Japanese Patent Laid-open Publication No. 170585/1991: HFC-32/125/134a, Japanese Patent Laid-open Publication No. 170584/1991: HFC-23/134a/152a, Japanese Patent Laid-open Publication No. 170583/1991: HFC-125/143a/32, Japanese Patent Laid-open Publication No. 222893/1992: HFC-32/125, Japanese Patent Laid-open Publication No. 154887/1992: HFC-134/152a, Japanese Patent Laid-open Publication No. 117645/1993: HFC-23/134a/propane, Japanese Patent Laid-open Publication No. 117643/1993: HFC-125/134a/propane, Japanese Patent Laid-open Publication No. 65561/1994: HFC-23/152a/PFC-218, Japanese Patent Laid-open Publication No. 128872/1994: HFC-32/PFC-218, Japanese Patent Laid-open Publication No. 220433/1994: HFC-32/125/RC-318, Japanese Patent Laid-open Publication No. 173462/1995: HFC-143a/125/134a/heptane (C₇H₁₆), Japanese Patent Laid-open Publication No. 176537/1996: PFC-218/RC-270/HFC-152a, Japanese Patent Laid-open Publication No. 151569/1996: propane/RC-270/HFC-134a, Japanese Patent Laid-open Publication No. 127767/1996: HFC-32/134a/RC-318, Japanese Patent Laid-open Publication No. 25480/1997: HFC-32/134a/125/isobutane, Japanese Patent Laid-open Publication No. 59611/1997: HFC-134a/isobutane, Japanese Patent Laid-open Publication No. 208941/1997: HFC-32/152a/125/RC-270, and Japanese Patent Laid-open Publication No. 221664/1997: HFC-125/143a/134a/RC-270.

Also, Korean Patent Publication No. 93-10514 (Application No. 90-19594) discloses a mixed refrigerant composition of HFC-23/32/152a, HFC-23/125/152a, HFC-32/143a/152a, HFC-125/143a/152a, HFC-32/125/125a, HFC-23/143a/152a, or HFC-23/125/152a, Korean Patent Publication No. 93-10515 (Application No. 90-19596) HFC-23/32/134, HFC-23/32/134a, HFC-23/125/134a, HFC-23/125/134, HFC-32/125/134, HFC-23/143a/134a, HFC-32/143a/134a, HFC-32/125/134a, HFC-125/143a/134a, or HFC-125/143a/134, Korean Patent Laid-open Publication No. 96-4485 (Application No. 95-21221) HFC-32/23/134a, Korean Patent Laid-open Publication No. 95-704438 (Application No. 95-701865) HFC-32/23/134a, Korean Patent Laid-open Publication No. 96-701168 (Application No. 95-704038) HFC-227ea/HFC-152a, and Korean Patent Laid-open Publication No. 97-704853 (Application No. 97-700436) HFC-134a/HCFC-124/butane.

SUMMARY OF THE INVENTION

Therefore, an object of the present invention is to provide a novel refrigerant mixture which is useful as a substitute for HCFC-22. That is, the present invention has an object to provide a refrigerant composition produced by mixing any one of RC-270, HFC-227ea, HFC-245cb, HFC-236ea, R-600, HFE-134, and HFE-245 with a mixture of HFC-32 and HFC-143a, thereby producing a composition capable of exhibiting properties similar to HCFC-22.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides a refrigerant composition which is useful as a substitute for HCFC-22, comprising a first constituent of difluoromethane (CH₂F₂, HFC-32); a second constituent of 1,1,1-trifluoroethane (CH₃CF₃; namely, HFC-143a); and a third constituent selected from the group consisting of cyclopropane (C₃H₆, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF₃CHFCF₃, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH₃CF₂CF₃, HFC-245cb), 1,1,1,2,3,3-hexafluoropropane (CHF₂CHFCF₃, HFC-236ea), butane (C₄H₁₀, R-600), bis(difluoromethyl)ether (CHF₂OCHF₂, HFE-134) and pentafluoroethylmethylether (CF₃CF₂OCH₃, HFE-245).

It is preferred that the refrigerant composition of the present invention comprises a first constituent of 10 to 70% by weight difluoromethane (CH₂F₂, HFC-32); a second constituent of 10 to 80% by weight 1,1,1-trifluoroethane (CH₃CF₃; namely, HFC-143a); and a third constituent of 0 to 50% by weight comprising one selected from the group consisting of cyclopropane (C₃H₆, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF₃CHFCF₃, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH₃CF₂CF₃, HFC-245cb), 1,1,1,2,3,3-hexafluoropropane (CHF₂CHFCF₃, HFC-236ea), butane (C₄H₁₀, R-600), bis(difluoromethyl)ether (CHF₂OCHF₂, HFE-134) and pentafluoroethylmethylether (CF₃CF₂OCH₃, HFE-245).

In accordance with the present invention, the refrigerant composition as mentioned above is applied to a refrigeration system which comprises a compressor, a condenser, an expansion valve, and an evaporator in order to evaluate the coefficient of performance (COP), value of calorie per volume of refrigerant (VC), and pressures in the compressor and evaporator. The novel refrigerant mixture according to the present invention is evaluated to be substantially equivalent to HFC-407C or HFC-410A in terms of performance. Accordingly, the refrigerant mixture of the present invention is useful as a substitute for HCFC-22.

Where the refrigerant mixture of the present invention includes HFC-32, HFC-143a, and RC-270, the composition comprises 10 to 50% by weight of HFC-32, 20 to 80% by weight of HFC-143a, and 0 to 40% by weight of RC-270. More preferably, the composition comprises 20 to 50% by weight of HFC-32, 30 to 70% by weight of HFC-143a, and 0 to 30% by weight of RC-270.

Where the refrigerant mixture of the present invention includes HFC-32, HFC-143a, and HFC-227ea, its composition comprises 20 to 80% by weight of HFC-32, 0 to 80% by weight of HFC-143a, and 0 to 60% by weight of HFC-227ea. Preferably, the composition comprises 30 to 70% by weight of HFC-32, 10 to 70% by weight of HFC-143a, and 0 to 45% by weight of HFC-227ea.

Where the refrigerant mixture of the present invention includes HFC-32, HFC-143a, and HFC-245cb, it is preferable that the refrigerant mixture has a composition comprises 20 to 70% by weight of HFC-32, 10 to 80% by weight of HFC-143a, and 0 to 40% by weight of HFC-245cb.

Where the refrigerant mixture of the present invention includes HFC-32, HFC-143a, and HFC-236ea, its composition comprises 20 to 70% by weight of HFC-32, 10 to 80% by weight of HFC-143a, and 0 to 30% by weight of HFC-236ea. Preferably, the composition comprises 30 to 60% by weight of HFC-32, 20 to 70% by weight of HFC-143a, and 0 to 20% by weight of HFC-236ea.

Where the refrigerant mixture of the present invention includes HFC-32, HFC-143a, and R-600, its composition comprises 20 to 60% by weight of HFC-32, 30 to 80% by weight of HFC-143a, and 0 to 20% by weight of R-600. Preferably, the composition comprises 30 to 50% by weight of HFC-32, 38 to 70% by weight of HFC-143a, and 0 to 12% by weight of R-600.

Where the refrigerant mixture of the present invention includes HFC-32, HFC-143a, and HFE-134, its composition comprises 20 to 70% by weight of HFC-32, 20 to 80% by weight of HFC-143a, and 0 to 15% by weight of HFE-134. More preferably, the composition comprises 30 to 60% by weight of HFC-32, 32 to 70% by weight of HFC-143a, and 0 to 8% by weight of HFE-134.

Where the refrigerant mixture of the present invention includes HFC-32, HFC-143a, and HFE-245, its composition comprises 20 to 80% by weight of HFC-32, 10 to 80% by weight of HFC-143a, and 0 to 20% by weight of HFE-245. More preferably, the composition comprises 30 to 70% by weight of HFC-32, 20 to 70% by weight of HFC-143a, and 0 to 10% by weight of HFE-245.

The present invention will be explained in more detail in the following examples. It is to be understood that these examples are merely illustrative and it is not intended to limit the scope of the present invention to these examples.

EXAMPLE

Evaluation of Performance of Refrigerant Mixture

In order to evaluate the performance of the refrigerant mixture according to the present invention, a refrigeration system including a compressor, a condenser, an expansion valve, and an evaporator was used which has the following performance evaluation conditions:

Refrigeration Capacity: 2 kW

Coefficient of Overall Heat Transfer coefficient in Evaporator (UA): 0.20 kW/K

Coefficient of Overall Heat Transfer coefficient in Condenser (UA): 0.24 kW/K

Degree of Subcooling in Condenser: 5° C.

Degree of Superheating in Evaporator: 5° C.

Efficiency of Compressor: 0.8

Temperature of Secondary Fluid at Inlet of Condenser: 25° C.

Temperature of Secondary Fluid at Outlet of Condenser: 35° C.

Temperature of Secondary Fluid at Inlet of Evaporator: 15° C.

Temperature of Secondary Fluid at Outlet of Evaporator: 5° C.

Under the above conditions, the refrigerant mixtures according to the present invention were compared to HCFC-22, HFC-407C, and HFC-410A in terms of the main factors for evaluating refrigerant performance, that is, the coefficient of performance (COP), value of calorie per volume of refrigerant (VC), and evaporator pressure (P_(L)), and condenser pressure (P_(H)).

Comparative Examples 1 to 3

HCFC-22, HFC-407C, and HFC-410A compared to the refrigerant compositions of the present invention have the following evaluated performances:

TABLE 1 Evaluated Performance of HCFC-22, HFC-407C, and HFC-410A HFC- Comparative HCFC-22 HFC-32 125 HFC-134a VC P_(L) P_(H) Example No. Refrigerant (wt. %) (wt. %) (wt. %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 HCFC-22 100 — — — 5.45 3338 455 1254 2 HFC-407C — 23 25 52 4.98 3412 460 1445 3 HFC-410A — 50 50 — 5.31 5117 730 1993

Referring to Table 1, it can be seen that HFC-407C exhibits a COP slightly less than that of HCFC-22 while exhibiting a VC and pressures similar to those of HCFC-22. On the other hand, HFC-410A has a COP similar to that of HCFC-22 while exhibiting pressures slightly higher than those of HCFC-22. It should be noted that a composition exhibiting a refrigerant performance defined as above is useful as a substitute refrigerant for HCFC-22. Accordingly, the performances of the refrigerant mixtures according to the present invention were evaluated and compared with the above evaluated results.

Example 1

Evaluation of Performance of Refrigerant Mixture of HFC-32/HFC-143a/RC-270

The evaluated performances of the refrigerant mixture comprising HFC-32/HFC-143a/RC-270 at different weight percent of each components are described in Table 2, respectively. Referring to Table 2, it can be found that the performance of the compositions indicated in each item of Table 2 fall within the ranges between those of HFC-407C and HFC-410A, so that the tested refrigerant mixture is useful as a substitute for HCFC-22.

TABLE 2 Evaluated Performance of Refrigerant Mixture of HFC-32/HFC-143a/ RC-270 Composi- tion HFC-32 HFC-143a RC-270 VC P_(L) P_(H) No. (wt. %) (wt. %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 20 60 20 4.98 4495 712 1893 2 40 30 30 5.00 4830 747 1992 3 35 35 30 4.98 4715 732 1959 4 30 50 20 5.06 4772 747 1967 5 25 65 10 5.03 4596 716 1917 6 30 70  0 5.11 4475 669 1831

Example 2

Evaluation of Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFC-227ea

The evaluated performances of the refrigerant mixture comprising HFC-32/HFC-43a/HFC-227ea at different weight percent of each components are described in Table 3, respectively. Referring to Table 3, it can be found that the performance of the compositions indicated in each item of Table 3 fall within the ranges between those of HFC-407C and HFC-410A, so that the tested refrigerant mixture is useful as a substitute for HCFC-22.

TABLE 3 Evaluated Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFC-227ea Com- po- sition HFC-32 HFC-143a HFC-227ea VC P_(L) P_(H) No. (wt. %) (wt. %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 40 40 20 5.15 4552 662 1844 2 35 35 30 5.01 4279 622 1797 3 40 20 40 4.99 4297 616 1810 4 60 20 20 5.39 5051 715 1927 5 70 10 20 5.46 5243 734 1962 6 45 10 45 5.00 4383 623 1838 7 30 50 20 5.02 4259 628 1786 8 30 60 10 5.08 4378 650 1809 9 30 70  0 5.11 4475 669 1831

Example 3

Evaluation of Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFC-245cb

The evaluated performances of the refrigerant mixture comprising HFC-32/HFC-143a/HFC-245cb at different weight percent of each components are described in Table 4, respectively. Referring to Table 4, it can be found that the performance of the compositions indicated in each item of Table 4 fall within the ranges between those of HFC-407C and HFC-410A, so that the tested refrigerant mixture is useful as a substitute for HCFC-22.

TABLE 4 Evaluated Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFC-245cb HFC- HFC- Composi- 32 143a tion (wt. (wt. HFC-245cb VC P_(L) P_(H) No. %) %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 40 40 20 5.10 4336 623 1772 2 40 50 10 5.18 4535 658 1819 3 40 55 5 5.20 4622 675 1848 4 40 30 30 5.01 4129 586 1722 5 60 20 20 5.30 4780 669 1850 6 30 60 10 5.05 4281 632 1775 7 50 20 30 5.13 4377 613 1770 8 30 70 0 5.11 4425 669 1831

Example 4

Evaluation of Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFC-236ea

The evaluated performances of the refrigerant mixture comprising HFC-32/HFC-143a/HFC-236ea at different weight percent of each components are described in Table 5, respectively. Referring to Table 5, it can be found that the performance of the compositions indicated in each item of Table 5 fall within the ranges between those of HFC-407C and HFC-410A, so that the tested refrigerant mixture is useful as a substitute for HCFC-22.

TABLE 5 Evaluated Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFC-236ea HFC- HFC- Composi- 32 143a tion (wt. (wt. HFC-236ea VC P_(L) P_(H) No. %) %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 30 60 10 4.99 4205 618 1765 2 60 30 10 5.32 4931 697 1899 3 60 20 20 5.02 4556 638 1858 4 40 50 10 5.11 4474 648 1818 5 50 40 10 5.23 4717 675 1861 6 30 70  0 5.11 4425 669 1831

Example 5

Evaluation of Performance of Refrigerant Mixture of HFC-32/HFC-143a/R-600

The evaluated performances of the refrigerant mixture comprisng HFC-32/HFC-143a/R-600 at different weight percent of each components are described in Table 6, respectively. Referring to Table 6, it can be found that the performance of the compositions indicated in each item of Table 6 fall within the ranges between those of HFC-407C and HFC-410A, so that the tested refrigerant mixture is useful as a substitute for HCFC-22.

TABLE 6 Evaluated Performance of Refrigerant Mixture of HFC-32/HFC-143a/R-600 Composi- tion HFC-32 HFC-143a R-600 VC P_(L) P_(H) No. (wt. %) (wt. %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 45 45 10 5.10 4611 687 1883 2 50 40 10 5.15 4740 702 1909 3 50 38 12 4.98 4551 676 1894 4 55 40 5 5.31 5007 731 1946 5 40 55 5 5.19 4673 696 1876 6 35 60 5 5.13 4545 682 1854 7 30 70 0 5.11 4425 669 1831

Example 6

Evaluation of Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFE-134

The evaluated performances of the refrigerant mixture comprisng HFC-32/HFC-143a/HFE-134 at different weight percent of each components are described in Table 7, respectively. Referring to Table 7, it can be found that the performance of the compositions indicated in each item of Table 7 fall within the ranges between those of HFC-407C and HFC-410A, so that the tested refrigerant mixture is useful as a substitute for HCFC-22.

TABLE 7 Evaluated Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFE-134 HFC- Composi- 32 tion (wt. HFC-143a HFE-134 FC P_(L) P_(H) No. %) (wt. %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 48 48 4 5.13 4574 654 1833 2 45 50 5 5.05 4438 635 1813 3 40 55 5 5.01 4341 625 1792 4 50 45 5 5.09 4535 645 1829 5 50 43 7 4.99 4388 619 1803 6 55 40 5 5.14 4623 653 1840 7 60 35 5 5.16 4702 660 1856 8 60 32 8 5.00 4479 624 1824 9 35 60 5 4.99 4240 614 1763 10 30 70 0 5.11 4425 669 1831

Example 7

Evaluation of Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFE-245

The evaluated performances of the refrigerant mixture comprisng HFC-32/HFC-143a/HFE-245 at different weight percent of each components are described in Table 8, respectively. Referring to Table 8, it can be found that the performance of the compositions indicated in each item of Table 8 fall within the ranges between those of HFC-407C and HFC-410A, so that the tested refrigerant mixture is useful as a substitute for HCFC-22.

TABLE 8 Evaluated Performance of Refrigerant Mixture of HFC-32/HFC-143a/HFE-245 HFC- Composi- 32 tion (wt. HFC-143a HFE-245 VC P_(L) P_(H) No. %) (wt. %) (wt. %) COP (kJ/m³) (kPa) (kPa) 1 70 20 10 5.03 4685 656 1890 2 65 25 10 4.98 4582 645 1874 3 60 35 5 5.35 4973 705 1902 4 50 45 5 5.22 4759 685 1878 5 40 55 5 5.13 4526 660 1833 6 30 65 5 4.99 4262 630 1784 7 30 70 0 5.11 4425 669 1831

As apparent from the above description, the present invention provides a refrigerant composition, which is useful as a substitute for HCFC-22, produced by mixing any one of RC-270, HFC-227ea, HFC-245cb, HFC-236ea, R-600, HFE-134 and PFC-245 with a mixture of HFC-32 and HFC-143a. The refrigerant composition according to the present invention has an advantage in that it does not damage the ozone layer, so there is no possibility of being restricted in use in the future. The above materials, which are components of the refrigerant composition according to the present invention, are currently commercially available, or active research for those materials is being conducted to make them commercially available in the future. Although the present embodiment of the present invention have been disclosed for illustrative purpose, those skilled in the art will appreciate that various modification, additions and substitutions are possible, without departing from the scope and spirit of the invention as recited in the accompanying claims. 

What is claimed is:
 1. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: a first constituent of difluoromethane; a second constituent of 1,1,1-trifluoroethane; and, a third constituent selected from the group consisting of cyclopropane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,2-pentafluoropropane, 1,1,1,2,3,3-hexafluoropropane, butane, bis(difluoromethyl)ether and pentafluoroethylmethylether.
 2. The refrigerant composition as claimed in claim 1, wherein the first constituent is 10 to 70% by weight, the second constituent is 10 to 80% by weight, and the third constituent is present in an amount up to 50% by weight.
 3. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: 20 to 40% by weight of difluoromethane, 30 to 70% by weight of 1,1,1-trifluoroethane, and, an amount up to 30% by weight of cyclopropane.
 4. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: 30 to 70% by weight of difluoromethane, 10 to 70% by weight of 1,1,1-trifluoroethane, and, an amount up to 45% by weight of 1,1,1,3,3,3-heptafluoropropane.
 5. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: 30 to 60% by weight of difluoromethane, 20 to 70% by weight of 1,1,1-trifluoroethane, and, an amount up to 30% by weight of 1,1,1,2,2-pentafluoropropane.
 6. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: 30 to 60% by weight of difluoromethane, 20 to 70% by weight of 1,1,1-trifluoroethane, and an amount up to 20% by weight of 1,1,1,2,3,3-hexafluoropropane.
 7. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: 30 to 50% by weight of difluoromethane, 38 to 70% by weight of 1,1,1-trifluoroethane, and, an amount up to 12% by weight of butane.
 8. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: 30 to 60% by weight of difluoromethane, 32 to 70% by weight of 1,1,1-trifluoroethane, and, an amount up to 8% by weight of bis(difluoromethyl)ether.
 9. A refrigerant composition useful as a substitute for chlorodifluoromethane, comprising: 30 to 70% by weight of difluoromethane, 20 to 70% by weight of 1,1,1-trifluoroethane, and, an amount up to 10% by weight of pentafluoroethylmethylether. 